Metallizable azo dyes prepared from a benzothiazole derivative and beta-naphthol



2,875,190 L METALLIZABLE AZO DYESMPREPARED FROM A BENZOTHIAZOLE AND B-NAPHTHOL Z M James M. Straley and Jolin G. Fisher,Kingsport, Tenm, assignors to Eastman KodalrCompany, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 15, 1957 Serial No. 652,689

7 Claimsor. 260-146) DERIYATIVE This invention relates to certain metallized azo dyes and their :application to the various materials. r a

The dyes of this inventionaremetallized complexes of azo dyes having the structural formula:

N OH

wherein X is selected from the group consisting of S and S r The non-metallized dyes that arel'employed in pre paring the dyes of this invention are preparedby diformulae uoomoncmzea'zotizing an amine having the structural V T G -NIH: HOCHaGHOHrX- wherein X is as defined above. I compound is then reacted or coupled with p-naphthol to form the non-metallized dyes of this invention. The nonmetallized dyes, after their preparation, are reacted with a metal salt, such as ,suitable salts of nickel,,coba lt, copper, chromium, manganese, iron or vanadium. .The nonmetallized azo compoundscan be metalliaedeither on or off the materials they color. Metallization can be car ried out, for example, bytreating the non-metallized azo compound with a solution or dispersion of the metallizing agent. Although the metal complex is often formed at room temperature, we preferto accelerate the process by heating, usually with steam, for a short period of time. The metallization is effected by procedures well known to those skilled in thelart to'. which thisfinvention is directed.

Illustrative of the metallizing agents that can be employed are the halides, the sulfates, thefacetates, the

cyanides and "the thiocyan'ates o'f nickeljcobalt, chromium, manganese, iron and .vanadium aswell as various copper compounds. .Thus, nickel .Jchloride, nickel bromide, nickel. sulfate,.nickelacetate, nickelx cyanide, nickel -formate, .nickel ,thiocyanate 1 [Ni(SCN) ,1 l; 0.0- baltous bromide, cobaltic chloride, cobaltous chloride,

cobaltous acetate, cobaltous cyanide, cobalt thiocyanate [Co(SCN) cupric chloride, cupric bromide, cupric acetate, cupric lactate, chromium trichloride, chromium tribromide, chromic sulfate, chromic acetate, chromium thiocyanate [Cr(SCN) manganese chloride, manganous sulfate, manganese acetate, manganese thiocyanate [Mn(SCN) ferric chloride, ferric fluoride, ferrous acetate, ferrous thiocyanate [Fe(SCN) ferric thiocyanate [Fe(SCN) and vanadium thiocyanate [V(SCN) are illustrative of the metallizing agents that can be employed. t

The non-metallized monoazo compounds described dyeing of cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, sulfone polyesters, polyethylene terephthalate and polyacrylonitrile. After application, to these materials, usually in. the form of textile herein are useful for the materials, the dye is metallized thereon. The metallized azo compounds of ourinvention can be applied by ordinary dyeing or printing techniques to nitrogenous textile materials such as wool, silk, nylon and acrylonitrilepolymers, for example. Coloration can also be effected by incorporating the non-metallized or metallized azo compounds into the spinning dope, spinning the fiber as usual and converting the non-metallized azo compounds to their metallized form. Also the metallizing 5 agent canbeincorporated in the spinning dope, the fiber dyeing or coloration of spun as .usual and then dyed with the non-metallized monoazo compounds to form the metal complex on the fiber. The new metallized dyes of our invention are preferably formed by heating the non-metallized azo dye with the metallizing agent inorganic solvents such as, for example, cellulose acetate, cellulose acetatepropidnate," acrylonitrile polymers, .polyamides, methyl cellosolve and formamide. As iswwell known, one ,ofthe disadvantages dyed cellulose acetatetextile fabrics suffer in comparison with some of the dyed competing textile fabrics, such as cotton, wool and viscose, for example, is lack of fastness to washing. Many schemes have been proposed to remedy this situationbut all' suffer from some significant fault. By means of I our invention dyed cellulose acetate textile .1: materials having,.good-to.excellent fastnessfito washing,

. pecially useful and particular claim is light and gas are obtainable. These results may be obtained by dyeing the ce11u1ose acetate textile material with the non-metallizedazb compounds and then treating the dyedcellulose acetate textile material with suitable metal salts which cause the original dye to form metallic complexes'which are resistant, for example, to the action of washing, light, and gas. These results can also be obtainedb'y incorporating the metallized azo dye into the cellulose acetate spinning dope and spinning the Thus; by means of the present invention, the disadvantage noted above with respect to the wash fastness of dyed cellulose acetate textile materials is either entirely or largely overcome. Cellulose acetate has been particularly referred to because it is the most' acid ester;

. .Whenthe metalcomplex is formed on carboxylic acid ester, such as cellulose useof a metal thiocyanate appears to be advantageous and is preferred. Nickel thiocyanate appears to be eslaid to its use. Next to nickel thiocyanate the use of cobalt thiocyanate is preferred. i

Metallization will be described in detail with reference to nickel andcobaltinasmuch as the metallized dyes containing thesefmaterials in complex combination appear to be advantageous. However, itwillbe clearly understood that thefnon-metalli zed azo compounds can be inetallized'with" the other metals disclosed herein. a The 'azo 'compoundsdisclosed herein have varying utility as dyes. The degree of utility varies, for example, depending upon the material being colored and the actual dye employed.

The following examples are illustrative of this invention:

Example 1 50 g. (0.242 m.) of Z-amino-G thiocyanobenzothiazole, 58 g. of N21 S-9H O, and 360 cc. of ethanol were refluxed 10 minutes. 26.7 g. of glycerin monochlorohydrin were added dropwise in about 15 minutes at reflux. After refluxing 1 hour longer, the solution was poured acetate fiber, the

into 1800 cc. of water and evaporated to a total volume I of 1.5 liters. Upon standing in the cold, crystals formed and were filtered off and washed with ice water. After drying in vacuo, there were obtained 53.4 g. of 2-amino- 6(B,'y dihydroxypropyltliio)benzothiazole, melting-lat 124-65 0.

9 g. (0.035 m.) of the productof Examplel were dissolved in 20 cc. of glacial acetic acid. After cooling toroom temperature, 10 cc. of 30% H 0 were'added, the temperature rising to about 65 C. The solution was evaporated to dryness in vacuo and theresidue recrystallized from 30 cc. of acetic acid. The yield was-82g. of 2 amino 6(B,'y dihydroxypropylsulfonyl)benzothiazole, melting at 200203 C.

Example 3 7.68 g. (0.03 m.) 'of the product of Example 1 were off and the oil boiled with 200cc. of methylcellosolve.

This solution was poured. into 1500 cc. ,of cold water with good stirring. The resultant solid was filtered off, washed with water, and air-dried. The yield was 10.25 g. of dye which, after treatment with nickel .thiocyanate on cellulose acetate, produced .deep blue dyeings of excellent resistance to the action of lightand laundering.

V Example 4 2.88 g. (0.01 m.),of the product of Example. 2 were dissolved in'a solution of 14;cc. of.-HSO in 24, ccr of water. After cooling to 0q-C. it'was 'diazotized wit 0.76 g. of NaNO in 5 cc. H SO 'asinExamp1e3. The diazo was run into a solution of 1.28 g. of-hydroquinone monomethyl ether in 20- cc. ofiwater below 5 C. The coupling was stirred 2 hours without-further cooling and the product filtered .off,,.washed, and dried in .air. Theyield was 3.1 g. of dye which, after reaction with nickel thiocyanate, imparts beautiful blue-green shades, to cellulose acetate.

Example .5

When cobalt thiocyanate was usedin Example 3fin place of nickel thiocyanate, the dye'wassomewhat' duller,

but of the same excellent light and wash fastness. Similar results were obtained when cobalt thiocyanate was. used in Example 4. Example 6 l g. of the non-metallized dye of Example 3 was stirred and refluxed in acetone. There wereiadded 3 cc. of 28% NH OH followedbya solution of 0.8 g. nickelous acetate crystals, in 16 cc. of acetone. After three hours reflux the mix was drowned in 400 cc. of water and the pigment filtered oflf, washed and dried. The product when incorporated in cellulose acetate yarn imparted deep shades of blue of excellent resistance to the action of light. 1

said monoazo compounds'having the'structural formula:

11 8 wherein X is selectedzfrom the group consisting of .S and S0 2. As a composition of matter, the azocompounds having the structuralformula:

N OH

t 7. As a composition, of matter, the nickel complex I of the 'azo'compound set forth in claim 6."

Reference s the fileof this patent i TATE P E 12,003,444 *Herzet' al. June 4, 1935 2,019,529 "Engelinann Nov. 5, 1935 2,686,176 Gunst- Aug. 10, 1954 

1. AS A COMPOSITION OF MATTER, THE AZO COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF MONOAZO COMPOUNDS AND THEIR METAL COMPLEXES IN COMBINATION WITH A METAL SELECTED FROM THE GROUP CONSISTING OF NICKEL, COBALT, COPPER, CHROMIUM, MANGANESE, IRON AND VANADIUM, SAID MONOAZO COMPOUNDS HAVING THE STRUCTURAL FORMULA: 